Reactions between benzylideneaniline (bzaH) or benzylidenemethylamine (bzmH) and MeM(CO)5(M = Mn or Re), PdCl2, Ru3(CO)12, or [Ru(CO)3Cl2]2, have afforded complexes containing ortho-metallated bza or bzm ligands. With [Rh(CO)2Cl]2 a variety of derivatives, including the rhodium(I)–rhodium(III) complex (bza)2Rh-µ-Cl2Rh(CO)2, and [(amine) Rh(CO)2Cl](amine = PhNH2 or bzmH), are formed.